Transparent thermoplastic molding composition, process for its preparation and its use

ABSTRACT

Transparent thermoplastic molding composition of a polymer containing 
     a) 10 to 95% by weight of units which are derived from a compound of the formula (I) 
     
         R.sub.2.sup.1 C═CF--COO--C(CF.sub.3).sub.2 R.sup.2     (I) 
    
     b) 90 to 5% by weight of units which are derived from one or more compounds of the formula (II) ##STR1##  and c) 0 to 85% by weight of units which are derived from a compound of the formula (III) 
     
         R.sub.2.sup.7 C═CF--COO--CR.sub.3.sup.8                (III) 
    
     The molding composition is used for the production of optical objects, in particular for the production of optical fibers.

Esters of 2-fluoroacrylic acid, in particular aromatic esters, and polymers of these compounds which are distinguished by high glass transition temperatures are described in the literature (DE-B-29 50 491). However, the transmission of light by these polymers is very low because of high degrees of light scattering and absorption. Optical materials which comprise polymeric 2-fluoroacrylic acid esters, in particular esters of aliphatic alcohols, which can contain deuterium atoms both in the alcohol component and in the β-position of the 2-fluoroacrylic acid component, are furthermore known (EP-A-128 517). The polymers described have refractive indices of between 1.45 and 1.60 and glass transition temperatures of between 100 and 200° C. and are used as core materials for optical fibers (polymeric optical fibers (POFs)). Polymeric 2-fluoroacrylic acid esters of fluorine-containing alcohols are employed as the cladding materials.

The preparation of poly(2-fluoroacrylic acid fluoroalkyl esters) is also known (EP-A 128 516).

The polymers are prepared by polymerization of the monomers, initiated by free radicals, in bulk, solution or suspension in the presence of a chain transfer agent at a temperature of between 0° and 100° C. They have refractive indices of between 1.36 and 1.44 and softening points of between 80° and 140° C.

Homo- and copolymers which contain 2-fluoroacrylic acid hexafluoroisopropyl ester and are used for the production of transparent objects are furthermore known (EP-B-203 402). Glass transition temperatures of 108° C. are given for the homopolymer, and of 140°, 142° and 133° C. for copolymers of the hexafluoroisopropyl ester and the methyl ester in weight ratios of 45:55, 66:34 and 79:21. Copolymers having a high content of the methyl ester (55 or 34 parts by weight of the methyl ester) have high transition temperatures, but also high refractive indices. However, their transparency to light is inadequate because of the carbon-hydrogen bonds present in the polymer and the high degrees of absorption caused by these.

Although the transparency of polymers to light can be increased by increasing the content of hexafluoroisopropyl ester (79 or 100 % by weight), this results in a drop in the glass transition temperature, so that this is no longer adequate for many fields of use of polymeric optical fibers.

The object of the invention was to provide a polymer comprising readily accessible monomers, which has high transparency to light in the wavelength range of visible light and at the same time a high glass transition temperature, and furthermore can be processed to a thermoplastic molding composition, and to optical fibers which are suitable for long transmission lengths and high long-term service temperatures.

The invention thus relates to a transparent, thermoplastic molding composition comprising a polymer containing

a) 10 to 95 % by weight of units which are derived from a compound of the formula (I)

    R.sup.1.sub.2 C═CF--COO--C(CF.sub.3).sub.2 R.sup.2     (I)

in which R¹ and R² are identical or different and are a hydrogen, deuterium or fluorine atom,

b) 90 to 5% by weight of units which are derived from one or more compounds of the formula (II) ##STR2## in which R³ is a hydrogen or deuterium atom,

R⁴ and R⁵ are identical or different and are a hydrogen or deuterium atom, a methyl or mono-, di- or trideuteromethyl group or a trifluoro- or tri-chloromethyl group and

R⁶ is a methyl or mono-, di- or trideuteromethyl or trifluoromethyl group, a phenyl group, a pentafluorophenyl group, a mono-, di- or trihalogenophenyl group, a mono-, di- or tri(perfluoro-C₁ to C₃ -alkyl)phenyl group or a CH₃ -CHF-CF₂ -CH₂ - group, a (CF₃)₃ C- group or an X-(CF₂)_(n) -(CH₂)_(m) - group, in which X is a hydrogen, deuterium, fluorine or chlorine atom, n is an integer from 2 to 4 and m is 0 or I, and

c) 0 to 85% by weight of units which are derived from a compound of the formula (III)

    R.sup.7.sub.2 C═CF--COO--CR.sup.8.sub.3                (III)

in which R⁷ and R⁸ are identical or different and are a hydrogen or deuterium atom,

the sum of (II) and (III), based on the total amount of the polymer, being in the range from 5 to 90% by weight.

The molding composition according to the invention contains (a) 10 to 95% by weight, preferably 40 to 95% by weight, particularly preferably 50 to 90% by weight of units which are derived from a compound of the formula (I). R¹ and R² here are identical or different and are a hydrogen, deuterium or fluorine atom, and R¹ is preferably a deuterium atom. Compounds of the formula (I) are particularly preferably d₃ -hexafluoroisopropyl 2-fluoroacrylates.

The molding composition furthermore contains (b) 90 to 5% by weight, preferably 60 to 5% by weight, particularly preferably 50 to 10% by weight of units which are derived from one or more compounds of the formula (II) in which R³ is a hydrogen or deuterium atom, preferably a deuterium atom;

R⁴ and R⁵ are identical or different and are a hydrogen or deuterium atom, a methyl or mono-, di- or trideuteromethyl group or a trifluoro- or trichloromethyl group, in particular a hydrogen or deuterium atom or a methyl or trideuteromethyl or trifluoromethyl group;

R⁶ is a methyl group, a mono-, di- or trideuteromethyl group, a trifluoromethyl group, a phenyl group, a pentafluorophenyl group, a mono-, di- or trihalogenophenyl group, a mono-, di- or tri(perfluoro-C₁ to C₃ -alkyl)phenyl group, a (CF₃ -CHF-CF₂ -CH₂ )- group, a (CF₃)₃ C- group or an X-(CF₂)_(n) -(CH₂)_(m) - group, in which X is a hydrogen atom, a deuterium atom, a fluorine atom or a chlorine atom, n can be 2, 3 or 4 and m can be 0 or 1, but in particular a methyl, mono-, di- or trideuteromethyl, trifluoromethyl, trichloromethyl, pentafluoro-n-propyl, 2,2,3,3-tetrafluoro-n-propyl, 2,2,3,3-tetrafluoro-n-propyl-d₃ or perfluoro-tert.-butyl group, and if appropriate (c) 0 to 85% by weight, preferably 0 to 65% by weight, particularly preferably 0 to 45% by weight of units which are derived from a compound of the formula (III). In formula (III), R⁷ and R⁶ are identical or different and are a hydrogen or deuterium atom, preferably a deuterium atom. The amounts by weight of the compounds of the formulae (II) and (III) add up to give, based on the total amount of the polymer, 5 to 90% by weight, preferably 5 to 60% by weight and particularly preferably 10 to 50% by weight.

The thermoplastic molding composition according to the invention contains, for example, the following compounds of the formula (II):

ethyl 2-fluoroacrylate,

trifluoroethyl 2-fluoroacrylate,

trichloroethyl 2-fluoroacrylate,

pentafluoropropyl 2-fluoroacrylate,

tetrafluoropropyl 2-fluoroacrylate,

isopropyl 2-fluoroacrylate,

trifluoroisopropyl 2-fluoroacrylate,

perfluoroisopropyl 2-fluoroacrylate,

perfluoro-(2,3-dimethyl-2-butyl) 2-fluoroacrylate,

trifluoro-tert.-butyl 2-fluoroacrylate,

trichloro-tert.-butyl 2-fluoroacrylate,

ethyl 2-fluoroacrylate-d₂,

trifluoroethyl 2-fluoroacrylate-d₂,

trichloroethyl 2-fluoroacrylate-d₂,

pentafluoropropyl 2-fluoroacrylate-d₂,

tetrafluoropropyl 2-fluoroacrylate-d₂,

isopropyl 2-fluoroacrylate-d₂,

trifluoroisopropyl 2-fluoroacrylate-d₂,

perfluoroisopropyl 2-fluoroacrylate-d₂,

perfluoro-(2,3-dimethyl-2-butyl) 2-fluoroacrylate-d₂,

trifluoro-tert.-butyl 2-fluoroacrylate-d₂,

trichloro-tert.-butyl 2-fluoroacrylate-d₂,

d₇ -ethyl 2-fluoroacrylate,

d₄ -trifluoroethyl 2-fluoroacrylate,

d₄ -trichloroethyl 2-fluoroacrylate,

d₄ -pentafluoropropyl 2-fluoroacrylate,

d₅ -tetrafluoropropyl 2-fluoroacrylate,

d₈ -isopropyl 2-fluoroacrylate,

d₉ isopropyl 2-fluoroacrylate,

d₈ trifluoroisopropyl 2-fluoroacrylate,

d₈ -trifluoro-tert.-butyl 2-fluoroacrylate or

d₈ -trichloro-tert.-butyl 2-fluoroacrylate.

Compounds of the formula (II) which are particularly preferably employed are:

d₇ -ethyl 2-fluoroacrylate,

d₄ -trifluoroethyl 2-fluoroacrylate

d₄ -trichloroethyl 2-fluoroacrylate,

d₄ -pentafluoropropyl 2-fluoroacrylate,

d₅ -tetrafluoropropyl 2-fluoroacrylate,

d₈ -isopropyl 2-fluoroacrylate,

d₆ -trifluoroisopropyl 2-fluoroacrylate,

d₉ -isopropyl 2-fluoroacrylate,

perfluoro-(2,3-dimethyl-2-butyl) 2-fluoroacrylate-d₂,

d₈ -trifluoro-tert.-butyl 2-fluoroacrylate and

d₈ -trichloro-tert.-butyl 2-fluoroacrylate.

In the units of the formula III, R⁷ is preferably a deuterium atom and R⁸ a hydrogen atom or a deuterium atom. The molding compositions contain in particular d₅ -methyl 2-fluoroacrylate.

The molding composition thus preferably contains

d₂ -hexafluoroisopropyl 2-fluoroacrylate or

d₃ -hexafluoroisopropyl 2-fluoroacrylate, and one or more compounds from the group comprising

ethyl 2-fluoroacrylate-d₂,

trifluoroethyl 2-fluoroacrylate-d₂,

trichloroethyl 2-fluoroacrylate-d₂,

pentafluoropropyl 2-fluoroacrylate-d₂,

tetrafluoropropyl 2-fluoroacrylate-d₂,

isopropyl 2-fluoroacrylate-d₂,

trifluoroisopropyl 2-fluoroacrylate-d₂,

perfluoroisopropyl 2-fluoroacrylate-d₂,

perfluoro-(2,3-dimethyl-2-butyl) 2-fluoroacrylate-d₂,

trifluoro-tert.-butyl 2-fluoroacrylate-d₂,

trichloro-tert.-butyl 2-fluoroacrylate-d₂,

d₇ -ethyl 2-fluoroacrylate,

d₄ -trifluoroethyl 2-fluoroacrylate,

d₄ -trichloroethyl 2-fluoroacrylate,

d₄ -pentafluoropropyl 2-fluoroacrylate,

d₅ -tetrafluoropropyl 2-fluoroacrylate,

d₈ -isopropyl 2-fluoroacrylate,

d₉ -isopropyl 2-fluoroacrylate,

d₆ -trifluoroisopropyl 2-fluoroacrylate,

d₈ -trifluoro-tert.-butyl 2-fluoroacrylate and

d₈ -trichloro-tert.-butyl 2-fluoroacrylate, and if appropriate from the group comprising

d₂ -methyl 2-fluoroacrylate or

d₅ -methyl 2-fluoroacrylate.

If appropriate, the molding composition can additionally contain units which are derived from compounds which can be copolymerized with the monomers of the formula I, formula II and formula III.

The monomers of the formulae I, II and III in particular can also additionally be copolymerized with other vinyl compounds. Such vinyl compounds which are particularly suitable are C₁ to C₆ alkyl esters of acrylic and methacrylic acid, in particular methyl methacrylate and d₈ -methyl methacrylate, and also styrene, styrene-d₈, styrene-d₅, pentafluorostyrene, vinyl chloride and vinyl acetate.

The weight ratio of the monomers of the formulae I, II and III to the other vinyl compounds employed as comonomers can be, for example, 60:40 to 99:1, preferably 80:20 to 99:1.

The molding compositions according to the invention can also be employed as a mixture with one another or with other polymeric molding compositions. They can be prepared by processes which are known per se, for example by suspension, emulsion, precipitation or bulk polymerization. The polymerization is preferably carried out in bulk with the aid of one or more initiators which act as free radicals. Examples of suitable initiators are azo compounds, such as azobisisobutyronitrile, azobis-(2,4,4-trimethylpent-2-ane) and azobis-tert.-butane, and organic peroxides, such as dicumyl peroxide, tert.-butyl peroxide, tert.-butyl peroctoate, tert.-butyl peroxyisopropylcarbonate, tert.-butyl hydroperoxide and tert.-butyl peroxyisobutyrate.

The amount of initiator is in the range from 0.001 to 3, preferably 0.001 to 0.3 mol per 100 mol of the monomers.

It is advantageous to carry out the polymerization in the presence of a chain transfer agent (regulator). Compounds which are particularly suitable for this are mercaptans, such as butyl mercaptan, tert.-butyl mercaptan, propylmercaptan, dodecylmercaptan, butanedithiol, pentanedithiol, phenylmercaptan, pentafluorophenylmercaptan and tert.-hexylmercaptan, and esters of mercaptoacetic acid, for example ethyl mercaptoacetate and ethylene glycol bis(mercaptoacetate).

The polymerization temperature is 20° to 180° C., preferably 50° to 150° C., particularly preferably 80° to 140° C.

The molding composition is obtained in the form of a glass-clear composition which can be deformed thermoplastically. The molding composition according to the invention has high glass transition temperatures, which are above 120° C., in particular above 130° C., particularly preferably in the range from 140° C. to 170° C., and thus surprisingly even sometimes exceed the glass transition temperatures both of the homopolymer which is derived from monomer units of the formula I and of the homopolymer which is derived from monomer units of the formula II.

Optical objects, in particular optical fibers, preferably optical fibers having a core/cladding structure, can be produced from the molding composition. The optical fibers can contain the molding composition according to the invention both in the core and in the cladding. When selecting the core and cladding material, it should be remembered that the maximum transition lengths for light signals in optical fibers is reached when the refractive indices of the core material n (C) and the cladding material n (S) of an optical fiber fulfill the following equations ##EQU1##

In a preferred embodiment, those copolymers which contain monomer units of the formulae I, II and III, in particular in which R¹, R³ and R⁷ are deuterium atoms, are employed as core materials. Copolymers which contain monomer units of the formulae I and II in which R¹, R² and R³, and R⁷ and R⁸ are deuterium atoms are particularly preferred. Copolymers which contain monomer units of the formula I in which R¹ and R² are a deuterium atom and one or more of the following compounds

d₇ -ethyl 2-fluoroacrylate,

d₄ -trifluoroethyl 2-fluoroacrylate,

d₄ -trichloroethyl 2-fluoroacrylate,

d₄ -pentafluoropropyl 2-fluoroacrylate,

d₅ -tetrafluoropropyl 2-fluoroacrylate,

d₈ -isopropyl 2-fluoroacrylate,

d₉ -isopropyl 2-fluoroacrylate,

d₆ -trifluoroisopropyl 2-fluoroacrylate,

perfluoro-(2,3-dimethyl-2-butyl) 2-fluoroacrylate-d₂,

d₈ -trifluoro-tert.-butyl 2-fluoroacrylate,

d₈ -trichloro-tert.-butyl 2-fluoroacrylate

or optionally d₅ -methyl 2-fluoroacrylate, are also particularly preferred.

Copolymers which contain monomer units which are derived from compounds of the formulae I, II and III can be employed as cladding materials. Those materials which have a relatively high content of monomer units of the formula I, preferably 40 to 85% by weight, particularly preferably 50 to 80% by weight, based on the total amount of the polymer, are particularly preferred here. Polymers which contain monomer units which are derived from fluoroalkyl esters, preferably from trifluoroethyl esters, pentafluoropropyl esters and hexafluoroisopropyl esters, or from perfluoro-2,3-dimethyl-2-butyl esters of 2-fluoroacrylic acid and of 2,3-difluoroacrylic acid are particularly suitable for use as cladding materials for the optical fibers according to the invention.

In another preferred embodiment, copolymers which contain monomer units which are derived from tetrafluoroethylene, from perfluoroalkyl vinyl ethers and from methyl perfluoro-3-oxa-4-pentene-1-carboxylate or from methyl perfluoro-4-oxa-5-hexene-1-carboxylate or from perfluoro-(dimethyldioxol) are employed as cladding material.

Optical fibers of the polymers according to the invention have an exceptionally good transmission of light, so that they can also be employed beyond the wavelength range of visible light, for example at 850 nm, so that long transmission lengths for light signals are additionally also rendered possible in such wavelength ranges.

Because of the high long-term service temperatures, optical fibers made from the materials according to the invention are particularly suitable for sectors where high temperature requirements are imposed on the materials, such as, for example, in the automobile industry.

EXAMPLES

Examples 1 to 3 and Comparison Examples V1 to V4

0.005% by weight of tert.-butyl peroxyisopropylcarbonate, 0.005% by weight of tert.-butyl hydroperoxide and butyl mercaptan were added to a mixture of hexafluoroisopropyl 2-fluoroacrylate (formula I, for the meaning of R¹ and R² see Table 1) and a 2-fluoroacrylic acid ester of the formula II (for the meaning of R³, R⁴, R⁵ and R⁶ see Table 1; the sum of monomers I and II gives 100% by weight) and the mixture was filtered by means of a membrane filter (pore width 45 nm) and introduced into a glass vessel which had been rinsed free from particles. The mixture was degassed by passing through helium gas (20 minutes), during which the oxygen partial pressure above the mixture was reduced to one thousandth of the saturation value (under standard conditions). The mixture was cooled to -78° C. in the helium atmosphere and evacuated. The glass vessel was then sealed off by melting and the product was heated first at 65° C. for 15 hours and then at 90° C. for 15 to 35 hours, until the composition had solidified in vitreous form. The bath temperature was then increased to 140° C. in the course of 10 hours for a further 24 hours. After the reaction mixture had been cooled, a glass-clear polymer which had the following properties (see Table 1) was obtained.

                                      TABLE 1                                      __________________________________________________________________________                                    Residual                                                                       monomer       Glass                                  Composition                                                                           Structure of the                                                                             Viscosity                                                                           content       transition                        Ex-  MR.sup.1 :I:II                                                                        monomer units No.  I  II   Refractive                                                                           temperature                       ample                                                                               (% by wt.)                                                                            R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                           R.sup.6                                                                           (in ml/g)                                                                           in % by wt.                                                                            index in °C.                     __________________________________________________________________________     1    0.5:30:70                                                                             H H H H H  CF.sub.3                                                                          89   0.01                                                                              <0.01                                                                               1.377 140                               2    0.5:60:40                                                                             H H H H H  CF.sub.3                                                                          76   0.08                                                                              <0.01                                                                               1.364 155                               3    0.5:85:15                                                                             H H H H H  CF.sub.3                                                                          55   0.1                                                                               <0.01                                                                               1.356 121                               4    0.5:40:60                                                                             H H H H CH.sub.3                                                                          CH.sub.3                                                                          60   0.02                                                                              0.25 1.366 121                               5    0.33:60:40                                                                            H H H H CH.sub.3                                                                          CH.sub.3                                                                          82   0.15                                                                              0.17 1.385 125                               6    0.2:70:30                                                                             H H H H CH.sub.3                                                                          CH.sub.3                                                                          120  0.1                                                                               0.05 1.397 121                               7    0.8:30:70                                                                             H H H H H  C.sub.2 F.sub.5                                                                   59   0.04                                                                              <0.01                                                                               1.365 129                               8    0.5:50:50                                                                             H H H H H  C.sub.2 F.sub.5                                                                   102  0.16                                                                              <0.01                                                                               1.361 142                               9    0.3:70:30                                                                             H H H H H  C.sub.2 F.sub.5                                                                   91   0.3                                                                               0.05 1.356 133                               Compar-                                                                        ison                                                                           Ex.                                                                            V1   0.5:100:0                                                                             H H --                                                                               --                                                                               -- -- 49   0.2                                                                               --   1.348 108                               V2   0.5:0:100                                                                             --                                                                               --                                                                               H H H  CF.sub.3                                                                          110  -- 0.26 1.38  104                               V3   0.5:0:100                                                                             --                                                                               --                                                                               H H CH.sub.3                                                                          CH.sub.3                                                                          88   -- 0.31 1.443  92                               V4   0.5:0:100                                                                             --                                                                               --                                                                               H H H  C.sub.2 F.sub.5                                                                   103  -- 0.05 1.371 105                               __________________________________________________________________________      .sup.1 Concentration of the molecular weight regulator (MR) in % by weigh      Example 1 to 3: butyl mercaptan                                                Examples 4 to 6: butyl dimercaptan                                             Examples 7 to 9: ethyl mercaptoacetate                                         Comparison Examples V1 to V4: butyl mercaptan                            

The viscosity number (in ml/g) was determined on solutions of the polymer (1% by weight) in ethyl acetate (99% by weight) at 25° C.

The residual monomer content (based on 100% by weight of the polymer) was determined by gas chromatography with the aid of an internal standard on solutions of 5% by weight of the polymer in 100% by weight of a suitable solvent.

The refractive index was measured with the aid of an Abbe refractometer on cast films which had been dried until the measurement value was constant and had been produced from solutions of the polymer in a suitable low-boiling solvent.

The glass transition temperature was determined by means of differential calorimetry (DSC) at a heating-up rate of 20° C./minute.

Examples 4 to 6

0.005% by weight of tert.-butyl peroxyisopropylcarbonate, 0.005% by weight of tert.-butyl hydroperoxide and butyl dimercaptan were added to a mixture of hexafluoroisopropyl 2-fluoroacrylate (formula I, for the meaning of R¹ and R² see Table 1) and isopropyl 2-fluoroacrylate (ester of the formula II, for the meaning of R³, R⁴, R⁵ and R⁶ see Table 1; the sum of I and II gives 100% by weight) in accordance with the data in Table 1. Further treatment of this mixture was carried out in a manner corresponding to the information on Examples 1 to 3.

Examples 7 to 9

0.005% by weight of tert.-butyl peroxyisopropylcarbonate, 0.005% by weight of tert.-butyl hydroperoxide and ethyl mercaptoacetate were added to a mixture of hexafluoroisopropyl 2-fluoroacrylate (formula I, for the meaning of R¹ and R² see Table 1) and pentafluoro-n-propyl 2-fluoroacrylate (ester of the formula II, for the meaning of R³, R⁴, R⁵ and R⁶ see Table 1; the sum of I and II gives 100% by weight) in accordance with the data in Table 1. Further treatment of this mixture was carried out in a manner corresponding to the information on Examples 1 to 3.

Comparison Examples V5 to V8

0.02% by weight of tert.-butyl peroxyisopropylcarbonate and 0.5% by weight of butyl mercaptan were added to a mixture of methyl 2-fluoroacrylate (formula III, for the meaning of R⁷ and R⁸ see Table 2) and an alkyl 2-fluoroacrylate of the formula II (for the meaning of R³, R⁴, R⁵ and R⁶ see Table 2). As described above, the mixture was filtered, introduced into a vessel, degassed and polymerized in a glass ampoule, which had been sealed off by melting, under the abovementioned conditions. After the reaction mixture had been cooled, a glass-clear polymer which had the following properties (see Table 2) was obtained.

The viscosity number was determined in acetone instead of in ethyl acetate.

                                      TABLE 2                                      __________________________________________________________________________                                  Residual                                                                       monomer     Glass                                     Composition                                                                           Structure of the                                                                            Viscosity                                                                           content     transition                            Ex- III:II monomer units                                                                               No.  III:II                                                                               Refractive                                                                           temperature                           ample                                                                              (% by wt.)                                                                            R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                          R.sup.6                                                                           R.sup.7                                                                          R.sup.8                                                                          (in ml/g)                                                                           in % by wt.                                                                          index in °C.                         __________________________________________________________________________     V5   30:70 H H H CF.sub.3                                                                          H H 165  0.03                                                                              0.14                                                                              1.402 121                                   V6   50:50 H H H CF.sub.3                                                                          H H 162  0.12                                                                              0.09                                                                              1.415 125                                   V7   70:30 H H H CF.sub.3                                                                          H H 168  0.10                                                                              0.05                                                                              1.434 131                                   V8  100:0  --                                                                               --                                                                               --                                                                               -- H H 182  0.02                                                                              -- 1.461 141                                   __________________________________________________________________________

Example 10 and 11

0.02% by weight of di-tert-butyl peroxide and 0.5% by weight of butyl mercaptan were added to a mixture of hexafluoroisopropyl 2-fluoroacrylate (HIFA, formula I where R¹ and R² are hydrogen), trifluoroethyl 2-fluoroacrylate (TEFA, formula II where R³, R⁴ and R⁵ are hydrogen and R⁶ is trifluoromethyl) and methyl 2-fluoroacrylate (MFA, formula III where R⁷ and R⁸ are hydrogen), which contains the three monomers as shown in Table 3 (sum=100% by weight). As described above, the mixture was filtered, introduced into a vessel, degassed and polymerized in a glass ampoule, which had been sealed off by melting, at a bath temperature of 85° C. as described under Example 1. The bath temperature was then increased to 140° C. After the reaction mixture had been cooled, a glass-clear polymer which had the following properties (see Table 3) was obtained.

                                      TABLE 3                                      __________________________________________________________________________     Composition    Viscosity                                                                           Residual monomer  Glass transition                         HIFA:TEFA:MFA  No.  content     Refractive                                                                           temperature                              Example                                                                             (% by wt) (in ml/g)                                                                           HIFA                                                                               TEFA                                                                               MFA index in °C.                            __________________________________________________________________________     10   60:35:5   75   0.15                                                                               0.08                                                                               0.02                                                                               1.366 148                                      11   70:10:20  71   0.22                                                                               0.05                                                                               0.11                                                                               1.374 149                                      __________________________________________________________________________

Examples 12 to 15

0.02% by weight of azobis(2,4,4-trimethylpent-2-ane), 0.005% by weight of tert.-butyl hydroperoxide and 0.5% by weight of butyl mercaptan were added to a mixture of hexafluoroisopropyl 2-fluoroacrylate (formula I, for the meaning of R¹ and R² see Table 4), another alkyl 2-fluoroacrylate of the formula II (for the meaning of R³, R⁴, R⁵ and R⁶ see Table 4) and methyl 2-fluoroacrylate (MFA, formula III, for the meaning of R⁷ and R⁸ see Table 4; the sum of the three monomers gives 100% by weight), and the mixture was filtered by means of a membrane filter (pore width 45 nm) and introduced into a glass vessel which had been rinsed free from particles. The mixture was degassed by bubbling argon gas through the mixture for a period of 40 minutes, during which the oxygen partial pressure above the mixture was reduced to one thousandth of the saturation value (under standard conditions). The mixture was cooled to - 78° C. in an argon atmosphere and evacuated. The glass vessel was then sealed off by melting and the product was first heated at 85° C. for 15 to 35 hours, until the composition in the ampoule had solidified in vitreous form. The bath temperature was then increased to 145° C. for a further 24 hours. After the reaction mixture had been cooled, a glass-clear polymer which had the following properties (see Table 4) was obtained.

                                      TABLE 4                                      __________________________________________________________________________                                        Residual                                                                       monomer    Glass                                 Composition              Viscosity                                                                           content    transition                       Ex-  I:II:III                                                                              Structure         No.  (sum, in                                                                            Refractive                                                                           temperature                      ample                                                                               (% by wt.)                                                                            R.sup.1                                                                          R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                           R.sup.6                                                                           R.sup.7                                                                          R.sup.8                                                                          (in ml/g)                                                                           % by wt.)                                                                           index in °C.                    __________________________________________________________________________     12   65:20:15                                                                              D H D H H  CF.sub.3                                                                          D H 73   0.22 1.371 149                              13   65:20:15                                                                              D D D H H  CF.sub.3                                                                          D D 72   0.28 1.371 149                              14   65:20:15                                                                              D D D D D  CF.sub.3                                                                          D D 73   0.23 1.373 151                              15   50:5:45                                                                               D D D D CD.sub.3                                                                          CD.sub.3                                                                          D D 83   0.35 1.398 145                              __________________________________________________________________________

Example 16

12.5 g of azobisisobutyronitrile (AIBN) were added to 10 kg of methyl ethyl ketone and 5 kg of hexafluoroisopropyl 2,3-difluoroacrylate, nitrogen gas was bubbled through and the mixture was stirred in a nitrogen atmosphere at 60° C. for 48 hours. The product was then precipitated in petroleum spirit (boiling range 60° to 80° C.) and collected by means of a filter. The product was then dried to constant weight and had the following properties:

    ______________________________________                                         Yield:                  91%                                                    Glass transition temperature:                                                                          95° C.                                          Refractive index:       1.341                                                  Viscosity number (1% strength                                                                          38 ml/g                                                by weight in 100% strength by                                                  weight ethyl acetate, 25° C.)                                           ______________________________________                                    

Example 17

Teflon AF 1600, a commercial product from DuPont comprising tetrafluoroethylene and perfluoro(dimethyldiol), was irradiated with 100 kGy of γ-radiation from a ⁶⁰ Co source. The polymer was then thermally after-treated at 250° C. in vacuo. The viscosity number (0.5% in Hostinert 272, a commercial product from Hoechst AG, as the solvent at 70° C.) decreased from 90 ml/g to 27 ml/g due to this treatment.

Example 18

A polymer which had been prepared as described in Example 2 was melted in a ram extruder and extruded to give the core of an optical fiber. The polymer according to Example 16 was fed into a twin-screw extruder with a degassing zone and processed to give the cladding of the optical fiber. The properties of the optical fiber are described in Table 5.

Example 19

A polymer which had been prepared as described in Example 8 was melted in a ram extruder and extruded to give the core of an optical fiber. A polymer which had been prepared as described in Example 17 was melted in a ram extruder, sintering together and processed to give the cladding of the optical fiber. The properties of the optical fiber are described in Table 5.

Example 20

A polymer which had been prepared as described in Example 12 was melted in a ram extruder and extruded to give the core of an optical fiber. A copolymer which is derived to the extent of 68% by weight from tetrafluoroethylene and to the extent of 32% by weight from perfluoropropyl vinyl ether (melt flow index: 13 g/10 minutes at 230° C.; 3.8 kg load) was fed into a twin-screw extruder with a degassing zone and processed to give the cladding of the optical fiber. The properties of the optical fiber are described in Table 5.

Example 21

A polymer which had been prepared as described in Example 13 was melted in a ram extruder and extruded to give the core of an optical fiber. A copolymer which is derived to the extent of 68% by weight from tetrafluoroethylene and to the extent of 32% by weight from perfluoropropyl vinyl ether (melt flow index: 13 g/10 minutes at 230° C.; 3.8 kg load) was fed into a twin-screw extruder with a degassing zone and processed to give the cladding of the optical fiber. The properties of the optical fiber are described in Table 5.

Example 22

A polymer which had been prepared as described in Example 14 was melted in a ram extruder and extruded to give the core of an optical fiber. A copolymer which is derived to the extent of 68% by weight from tetrafluoroethylene to the extent of 68% by weight from tetrafluoroethylene and to the extent of 32% by weight from perfluoropropyl vinyl ether (melt flow index: 13 g/10 minutes at 230° C.; 3.8 kg load) was fed into a twin-screw extruder with a degassing zone and processed to give the cladding of the optical fiber. The properties of the optical fiber are described in Table 5.

Example 23

A polymer which had been prepared as described in Example 15 was melted in a ram extruder and extruded to give the core of an optical fiber. A polymer which had been prepared as described in Example 3 was melted in a ram extruder and processed to give the cladding of the optical fiber. The properties of the optical fiber are described in Table 5.

Example 24

A polymer which had been prepared as described in Example 11 was melted in a ram extruder and extruded to give the core of an optical fiber. A copolymer which is derived to the extent of 60% by weight from tetrafluoroethylene, to the extent of 34% by weight from perfluoropropyl vinyl ether and to the extent of 6% by weight from methyl perfluoro-3-oxy-4-pentene-1-carboxylate (melt flow index: 13 g/10 minutes at 230° C.; 3.8 kg load) was fed into a twin-screw extruder with a degassing zone and processed to give the cladding of the optical fiber. The properties of the optical fiber are described in Table 5.

                  TABLE 5                                                          ______________________________________                                              Damp-   Damp-   Damping at 650 nm                                                                          Damping at 650 nm                             Ex-  ing     ing     after 2 hrs in a                                                                           after the                                     am-  650 nm  830 nm  heating cabinet                                                                            bending test                                  ple  dB/km   dB/km   dB/km °C.                                                                             in dB/km                                    ______________________________________                                         18   50              55    110     90                                          19   45              54    110     48                                          20   44      129     70    110     61                                          21   30      84      46    110     52                                          22   25      37      51    110     40                                          23   27      35      39    110     40                                          24   55              58    110     65                                          ______________________________________                                    

The damping was determined on pieces of the optical fiber 30 m long by feeding in light of a wavelength (650 nm, 830 nm) from one end of the optical fiber and measuring the light intensity at the other end as a function of the length of the optical fiber, which was shortened by a certain length after each measurement. A logarithmic plot of the light intensities against the length of the optical fiber in km gives the damping D as the gradient according to the following equation: ##EQU2## L₁ =Length of the unshortened optical fiber L₂ =Length of the shortened optical fiber

I.sub.(L) =Transmitted light intensity as a function of the length of the optical fiber.

To test the heat resistance, a section of the optical fiber was in each case kept at the stated temperatures in normal ambient air for two hours and the damping was then measured.

To test the flexural strength ("bending test"), an optical fiber 20 m long (diameter 0.5 mm) was clamped in the damping measuring device, the damping was determined and a section of this optical fiber 150 cm long (L=150) was wound round a rod of 30 mm diameter. The optical fiber was removed again from the rod and straightened out. The transmitted light intensity was then measured again and the increase in damping as a result of the deformation of the optical fiber (D_(Def)), expressed in dB/km, was added to the damping of the undamaged optical fiber. ##EQU3## I_(before) =transmitted light intensity before the deformation I_(after) =transmitted light intensity after the deformation 

We claim:
 1. An optical fiber having a core/cladding structure, the core of which comprises a polymer of refractive index n(C) and the cladding of which comprises a polymer of refractive index n(S), in which n(C)/n(S)>1.01, in which the core of the optical fiber comprises a molding composition of a polymer containinga) 10 to 95% by weight of units which are derived from a compound of the formula (I)

    R.sup.1.sub.2 C═CF--COO--C(CF.sub.3).sub.2 --R.sup.2   (I)

in which R¹ and R² are identical or different and are a hydrogen, deuterium or fluorine atom, b) 90 to 5% by weight of units which are derived from one or more compounds of the formula (II) ##STR3## in which R³ is a hydrogen or deuterium atom, R⁴ and R⁵ are identical or different and are a hydrogen or deuterium atom, a methyl or mono-, di- or trideuteromethyl group or a trifluoro- or trichloromethyl group; R⁶ is a methyl or mono-, di- or trideuteromethyl or trifluoromethyl group, a phenyl group, a pentafluorophenyl group, a mono-, di- or trihalogenophenyl group, a mono-, di- or tri(perfluoro-C₁ to C₃ -alkyl)phenyl group or a CF₃ -CHF-CF₂ -CH₂ - group, a (CF₃)₃ C- group or an X-(CF₂)_(n) -(CH₂)_(m) - group, in which X is a hydrogen, deuterium, fluorine or chlorine atom, n is an integer from 2 to 4 and m is 0 or 1, and c) 0 to 85% by weight of units which are derived from a compound of the formula (III)

    R.sup.7.sub.2 C═CF--COO--CR.sup.8.sub.3                (III)

in which R⁷ and R⁸ are identical or different and are a hydrogen or deuterium atom, the sum of (II) and (III), based on the total amount of the polymer, being in the range from 5 to 90% by weight.
 2. An optical fiber as claimed in claim 1, in which the cladding comprises a polymer which contains units which are derived from fluoroalkyl esters of 2-fluoroacrylic acid.
 3. An optical fiber as claimed in claim 1, in which the cladding comprises a polymer which contains units which are derived from fluoroalkyl esters of 2,3-difluoroacrylic acid.
 4. An optical fiber as claimed in claim 1, in which the cladding contains polymers which are derived from hexafluoroisopropyl 2-fluoroacrylate.
 5. An optical fiber as claimed in claim 1, in which the cladding comprises a polymer which contains units which are derived from tetrafluoroethylene, from perfluoroalkyl vinyl ethers or from methyl perfluoro-3-oxa-4-pentene-1-carboxylate, methyl perfluoro-4-oxa-5-hexene-1-carboxylate or from perfluoro(dimethyldioxol).
 6. The optical fiber as claimed in claim 1, wherein the cladding comprises a copolymer which contains units which are derived from tetrafluoroethylene and from perfluoro(dimethyldioxol).
 7. An optical fiber having a core/cladding structure, the core of which comprises a polymer of refractive index n(C) and the cladding of which comprises a polymer of refractive index n(S), in which n(C)/n(S)>1.01, in which the core of the optical fiber comprises a molding composition of a polymer containinga) 10 to 95% by weight of units which are derived from a compound of the formula (I)

    R.sup.1.sub.2 C═CF--COO--C(CF.sub.3).sub.2 --R.sup.2   (I)

in which R¹ and R² are identical or different and are a hydrogen, deuterium or fluorine atom; b) 90 to 5% by weight of units which are derived from one or more compounds of the formula (II) ##STR4## in which R³, R⁴ and R⁵ are H and R³ is CF₃ ; and c) 0 to 85% by weight of units which are derived from a compound of formula (III)

    R.sup.7.sub.2 C═CF--COO--CR.sup.8.sub.3                (III)

in which R⁷ and R⁸ are identical or different and are a hydrogen or deuterium atom,the sum of (II) and (III) based on the total amount of the polymer being in the range from 5 to 90% by weight. 